The present invention relates to coating compositions for metal substrates, methods of coating a metal substrate, and metal articles having a coating composition applied thereon. The coating composition comprises: (a) an acrylate copolymer having pendant hydroxy groups, (b) a hydroxy-terminated polyester, and (c) a crosslinker in (d) a nonaqueous carrier, and is free of a halide-containing vinyl polymer. The coating composition, after curing, is useful as a topcoat for the interior of metal closures and demonstrates excellent flexibility and adhesion to primer coats and to plastisol gaskets.
It is well known that an aqueous solution in contact with an untreated metal substrate can result in corrosion of the untreated metal substrate. Therefore, a metal article, such as a metal closure or container for a water-based product, like a food or beverage, is rendered corrosion resistant in order to retard or eliminate interactions between the water-based product and the metal article. Generally, corrosion resistance is imparted to the metal article, or to a metal substrate in general, by passivating the metal substrate or by coating the metal substrate with a corrosion-inhibiting coating.
Investigators continually have sought improved coating compositions that reduce or eliminate corrosion of a metal article and that do not adversely affect an aqueous product packaged in the metal article. For example, investigators have sought to improve the imperviousness of the coating in order to prevent corrosion-causing ions, oxygen molecules, and water molecules from contacting and interacting with a metal substrate. Imperviousness can be improved by providing a thicker, more flexible, and more adhesive coating, but often improving one particular advantageous property is achieved at the expense of another advantageous property.
In addition, practical considerations limit the thickness, adhesive properties, and flexibility of a coating applied to a metal substrate. For example, thick coatings are expensive, require a longer cure time, can be esthetically unpleasing, and can adversely affect the process of stamping and molding the coated metal substrate into a useful metal article. Similarly, the coating should be sufficiently flexible such that the continuity of the coating is not destroyed during stamping and molding of the metal substrate into the desired shape of the metal article.
Investigators also have sought coatings that possess chemical resistance in addition to corrosion inhibition. A useful coating for the interior of a metal closure or container must be able to withstand the solvating properties of the packaged product. If the coating does not possess sufficient chemical resistance, components of the coating can be extracted into the packaged product and adversely affect the product. Even small amounts of extracted coating components can adversely affect sensitive products, such as beer, by imparting an off-taste to the product.
Organic solvent-based coating compositions provide cured coatings having excellent chemical resistance. Such solvent-based compositions include ingredients that are inherently water insoluble, and, thereby, effectively resist the solvating properties of water-based products packaged in the metal container.
Epoxy-based coatings and polyvinyl chloride-based coatings have been used to coat the interior of metal closures and containers for foods and beverages because these coatings exhibit an acceptable combination of adhesion, flexibility, chemical resistance, and corrosion inhibition. Polyvinyl chloride-based coatings and vinyl acetate/vinyl chloride copolymer-based (i.e., solution vinyl) coatings also have been the topcoat of choice for the interior of metal closures because these coatings provide excellent adhesion to plastisol sealer gaskets applied over the cured topcoat. However, epoxy-based coatings and polyvinyl chloride-based coatings have serious disadvantages that investigators still are attempting to overcome.
For example, polyvinyl chloride-based coating compositions are thermoplastic. Thermoplastic coatings used as the topcoat of the interior coating of metal closures have inherent performance disadvantages, such as potential softening during the closure manufacturing process or under food processing conditions. Therefore, coating compositions having a thermosetting character have been investigated.
In addition, coatings based on polyvinyl chloride or a related halide-containing vinyl polymer, like polyvinylidene chloride, possesses the above-listed advantageous properties of chemical resistance and corrosion inhibition, and are economical. However, curing a polyvinyl chloride or related halide-containing vinyl polymer can generate toxic monomers, such as vinyl chloride, a known carcinogen. In addition, the disposal of a halide-containing vinyl polymer, such as by incineration, also can generate toxic monomers. The generated vinyl chloride thereby poses a potential danger to workers in metal can and closure manufacturing plants, in food process and packaging plants, and at disposal sites. Disposal of polyvinyl chloride and related polymers also can produce carcinogenic dioxins and environmentally harmful hydrochloric acid.
Government regulators are acting to eliminate the use of polyvinyl chloride-based coating compositions that contact food, and thereby eliminate the environmental and health concerns associated with halide-containing vinyl polymers. Presently, however, polyvinyl chloride-based compositions are still used to coat the interior of food and beverage containers and closures.
To overcome the environmental concerns and performance problems associated with polyvinyl chloride-based coating compositions, epoxy-based coating compositions recently have been used to coat the interior of food and beverage containers. However, epoxy-based coatings also possess disadvantages. For example, epoxy-based coating compositions are more expensive than polyvinyl chloride-based coating compositions.
In addition, epoxy-based coatings are prepared from monomers such as bisphenol A and bisphenol A diglycidyl ether (BADGE), for example. 
Epoxy resins have a serious disadvantage in that residual amounts of glycidyl ether and bisphenol monomers are present in the resin, typically in an amount of about 0.5% by weight. The presence of such monomers, and especially a glycidyl ether monomer, raises serious environmental and toxicological concerns, especially because a glycidyl ether monomer can be extracted from a cured coating on the interior of a metal container by a product stored in the container. Accordingly, regulatory agencies have promulgated regulations reducing the amount of a glycidyl ether monomer in coating compositions, and especially coating compositions used on the interior of food and beverage containers.
Coating compositions also typically include a phenolic resin. Phenolic resins prepared from bisphenol A or similar bisphenols also can contain residual bisphenol monomers, similar to epoxy-based coatings. Phenolic resins also have disadvantages in that the resins can generate formaldehyde, which can adversely affect a product stored in a coated metal container. Accordingly, it would be an advance in the art to overcome the problems and disadvantages associated with coating compositions for metal substrates that contain an epoxy resin, a halide-containing vinyl polymer, and/or a phenolic resin.
With respect to a metal closure for a food container, the interior of a metal closure conventionally can be coated with three separate coating compositions, i.e., a three-coat system. First, an epoxy/phenolic primer is applied to the metallic substrate and cured, then a vinyl-based middle coat is applied over the cured primer. Finally, after curing the middle coat, a specially formulated topcoat capable of adhering to a plastisol sealer is applied over the cured middle coat. The plastisol sealer is applied over the cured topcoat, and formed into a gasket during manufacture of a metal closure from a metal sheet having the three cured layers of coatings applied thereon.
Two-coat systems are the primary commercial system, but also exhibit disadvantages. A two-coat system for the interior of metal food closure comprises a primer (i.e., a size) and a topcoat. The metal closures typically are used in conjunction with a glass or plastic container. The topcoat must have sufficient adhesion to the primer or the coating will fail. In order to achieve sufficient intercoat adhesion, the chemical makeup of the topcoat often was dictated by the chemical make-up of the primer. Investigators, therefore, are attempting to develop an improved two-coat system for coating the interior of a metal closure, for example, a more xe2x80x9cuniversalxe2x80x9d topcoat, i.e., a topcoat that can be applied to a variety of different primers and that exhibits sufficient intercoat adhesion. Such a universal topcoat would be a significant advance in the art.
Two-coat systems have been investigated and used for application to the interior of metal closures. Investigators sought and used topcoat compositions having a sufficiently flexible cured coating such that a coated metal substrate can be deformed without destroying film continuity. This is an important property because the metal substrate is coated prior to deforming, i.e., shaping, the metal substrate into a metal article, like a metal closure. Coating a metal substrate prior to shaping the metal substrate is the present standard industrial practice.
An ideal two-coat system maintains corrosion inhibition, lowers the cost of applying the coatings, has improved rheological properties, has improved cured film integrity, is free of a polyvinyl chloride-based resin, residual bisphenol monomers, and residual glycidyl ether monomers. In addition, it would be desirable to provide a top coat that acts as a barrier against the migration of bisphenol and glycidyl ether monomers from an epoxy resin-based primer coat.
The coatings used on the interior of a metal food closure also must meet other criteria in addition to performance. For example, the coatings must incorporate components acceptable to the U.S. Food and Drug Administration (FDA) because the cured coating composition contacts food products.
The cured primer and topcoat also require sufficient adhesion to maintain film integrity during closure fabrication. The cured primer and topcoat further require sufficient flexibility to withstand closure fabrication. Sufficient coating adhesion and flexibility also are needed for the closure to withstand processing conditions the closure is subject to during product packaging. Other required performance features of the cured coatings include corrosion protection and adequate adhesion to the plastisol gasket applied over the cured topcoat, sufficient chemical resistance, and sufficient abrasion and mar resistance.
In the manufacture of a metal closure, a metal sheet is coated with the coating compositions, and each coating is cured individually, then the metal sheet is formed into the shape of a metal closure. The closures are made in a variety of sizes ranging from 27 mm (millimeter) to 110 mm in diameter. During manufacture, a plastisol material is applied over the cured coatings on the interior of the metal closure. This plastisol subsequently is formed into a gasket and cured. The gasket ensures an effective seal between the metal closure and glass container, and maintains the vacuum condition of the packaged food product.
Product packaging is performed under processing conditions wherein the plastisol gasket is softened. When the metal closure is pressed onto the glass container, the threads on the glass container form impressions in the softened plastisol gasket. The metal closure is secured in place both by the thread impressions and by the vacuum produced by subsequent cooling. This type of metal closure is used for baby food containers and for other packaged food and beverage products, such as juices and gravies. Other types of closures are designed to be secured to glass containers by lugs rather than by thread impressions in the plastisol.
Vinyl chloride-based topcoat compositions have been softened both by product processing conditions, and by conditions encountered during closure manufacture, thereby leading to closure failure.
The present invention is directed, in part, to overcoming such closure failures, and provide an improved two-coat system for the interior of metal closures used for vacuum-packed food products.
Investigators have particularly sought a vinyl halide-free topcoat for the interior of metal closures for food and beverages that retains the advantageous properties of a vinyl chloride-based topcoat, such as adhesion, flexibility, chemical resistance, corrosion inhibition, and favorable economics. Investigators especially have sought a coating composition that demonstrates these advantageous properties and also reduces the environmental and toxicological concerns associated with halide-containing vinyl polymers, formaldehyde, and residual glycidyl ether and bisphenol monomers.
A present topcoat coating composition includes: (a) an acrylate copolymer having pendant hydroxyl groups, typically a hydroxyalkyl (meth)acrylate-alkyl (meth)acrylate copolymer, (b) a hydroxy-terminated polyester, and (c) a crosslinker, wherein the composition is free of a halide-containing vinyl polymer, and which, after curing, demonstrates: (1) excellent flexibility, (2) excellent adhesion to the primer coat, (3) excellent chemical resistance and corrosion inhibition, (4) excellent adhesion to the plastisol gasket, and (5) reduced environmental and toxicological concerns.
As an added advantage, a present topcoat coating composition provides an improved two-coat system, thereby eliminating the presence of a halide-containing vinyl polymer and the presence of residual bisphenol and glycidyl ether monomers, while providing an effective barrier against migration of residual bisphenol and glycidyl ether monomers from the size coat. The present topcoat coating composition also can be used with a variety of types of primers without a significant decrease in coating properties.
The present invention is directed to a coating composition that, after curing, effectively inhibits corrosion of metal substrates, is flexible, and exhibits excellent adhesion both to a primer coat and to a variety of plastisol gaskets used to ensure the vacuum seal of a metal closure to a glass container. The present coating composition comprises: an acrylate copolymer having pendant hydroxy groups, a hydroxy-terminated polyester, and a crosslinker in a nonaqueous carrier. The present coating composition also is free of (a) a halide-containing vinyl polymer, such as polyvinyl chloride, (b) formaldehyde, and (c) glycidyl ether and bisphenol monomers, such as BADGE and bisphenol A, used in the preparation of an epoxy resin. Nevertheless, after curing and crosslinking, the coating compositions demonstrate excellent adhesion both to a primer coat and to a plastisol gasket.
The coating compositions effectively inhibit corrosion of ferrous and nonferrous metal substrates when a composition is applied as a topcoat to a metal substrate, then cured for a sufficient time and at a sufficient temperature to provide a crosslinked coating. A cured and crosslinked coating demonstrates sufficient chemical and physical properties for use as the topcoat of a two-coat system on the interior of metal closures used in packaging foods and beverages. The coating composition does not adversely affect products packaged in a container having a metal closure coated on the interior surface with the cured composition.
In particular, the present coating composition comprises: (a) about 45% to about 90%, by weight of nonvolatile material, of an acrylate copolymer having pendant hydroxy groups, for example, a hydroxyalkyl (meth)acrylate-alkyl (meth)acrylate copolymer, (b) about 10% to about 40%, by weight of nonvolatile material, of a hydroxy-terminated polyester, and (c) about 1% to about 15%, by weight of nonvolatile material, of a crosslinker, wherein the composition is free of a halide-containing vinyl polymer. The weight ratio of hydroxy-containing monomers, e.g., a hydroxyalkyl (meth)acrylate, to alkyl (meth)acrylate in the copolymer is about 1:1 to about 1:50.
Components (a), (b), and (c) are dispersed in a nonaqueous carrier such that the total coating composition includes about 20% to about 80%, by weight of the total composition, of components (a), (b), and (c). Other optional components, such as a curing catalyst, a pigment, a filler, or a lubricant, also can be included in the composition, and, accordingly, increase the weight percent of total nonvolatile material in the composition to above about 80% by weight of the total coating composition.
As used here and hereinafter, the term xe2x80x9ccoating compositionxe2x80x9d is defined as the composition including the acrylate copolymer having pendant hydroxy groups, the hydroxy-terminated polyester, the crosslinker, and any optional ingredients dispersed in the nonaqueous carrier. The term xe2x80x9ccured coating compositionxe2x80x9d is defined as the adherent polymeric coating resulting from curing a coating composition. The cured coating composition comprises the acrylate copolymer having pendant hydroxy groups, the hydroxy-terminated polyester, and the crosslinker essentially in the amounts these ingredients are present in the coating composition, expressed as nonvolatile material.
Therefore, one important aspect of the present invention is to provide a coating composition that enhances the ability of the primer to inhibit corrosion of ferrous and nonferrous metal substrates. After application to a primed metal substrate as a topcoat, and subsequent curing at a sufficient temperature for a sufficient time, the coating composition provides an adherent layer of a cured coating composition. The cured coating composition enhances corrosion inhibition, has excellent flexibility, and exhibits excellent adhesion both to a variety of different of primer types applied to the metal substrate and to a variety of different types of plastisol sealer gaskets applied over the cured coating composition.
Because of these properties, an improved two-coat system is available for application to the metal substrate thereby providing economies in time, material, and machinery in the coating of a metal substrate. The coating composition also provides economies because the composition can be used with a variety of primers and plastisol gaskets of different chemical types. The closure manufacturer, therefore, can use the coating composition in a more universal range of applications, which eliminates the need to stock an inventory of different topcoats and eliminates application equipment changeover.
In accordance with another important aspect of the present invention, a cured coating composition demonstrates excellent flexibility and adhesion with respect to the plastisol sealer gasket. The excellent adhesion between the cured coating composition and the plastisol sealer gasket further improves the vacuum seal between a metal closure and a glass container to maintain product integrity, and the excellent flexibility facilitates processing of the coated metal substrate into a coated metal article, like in molding or stamping process steps, such that the cured coating remains in continuous and intimate contact with the primer on the metal substrate.
In accordance with yet another important aspect of the present invention, the cured coating composition demonstrates an excellent flexibility and adhesion even though the coating composition does not include a halide-containing vinyl polymer. Conventional coating compositions include a polyvinyl chloride to impart flexibility to the cured coating and to provide adhesion to the plastisol gasket. However, the presence of polyvinyl chloride adversely affects the heat resistance of the cured composition. A present coating composition, which excludes a halide-containing vinyl polymer (and glycidyl ether and bisphenol monomers), has excellent heat resistance, and, surprisingly, excellent flexibility.
In accordance with yet another important aspect of the present invention, a primed metal substrate coated on at least one surface with a cured coating composition of the present invention can be formed into a metal closure for a glass or plastic container that holds food products. Conventionally, a particular type of topcoat was applied over a particular primer in order to achieve sufficient intercoat adhesion. The present coating composition overcomes this disadvantage, and provides a cured coating composition that exhibits sufficient intercoat adhesion with a variety of types of primers, and with a variety of types of plastisol sealers.
These and other aspects and advantages of the present invention will become apparent from the following detailed description of the preferred embodiments.
A coating composition of the present invention, after curing, provides a cured coating composition that effectively enhances corrosion inhibition of primed metal substrates, such as, but not limited to, aluminum, iron, steel, and copper. A present coating composition, after curing, also demonstrates excellent adhesion to the primer coat applied to the metal substrate and to a plastisol gasket, excellent chemical and scratch resistance, and excellent flexibility.
Accordingly, a coat between the primer and topcoat, i.e., the middle coat, can be eliminated. The present coating compositions, therefore, are useful in an improved two-coat system comprising a primer and a topcoat. The present coating compositions are especially useful as the topcoat of a two-coat system for the interior of a metal closure for vacuum-packed food products, because the topcoat is free of a vinyl halide-containing polymer, residual bisphenol monomers, and residual glycidyl ether monomers, and provides an effective barrier against the migration of residual bisphenol and glycidyl ether monomers from the size coat.
A present coating composition comprises: (a) an acrylate copolymer having pendant hydroxy groups, typically a hydroxyalkyl (meth)acrylate-alkyl (meth)acrylate copolymer, (b) a hydroxy-terminated polyester, (c) a crosslinker, and (d) a nonaqueous carrier. A coating composition of the present invention is free of a halide-containing vinyl polymer, formaldehyde, and glycidyl ether and bisphenol monomers, like bisphenol A and BADGE. In addition, a present coating composition can include optional ingredients, like a catalyst or pigment, that improve the esthetics of the composition, that facilitate processing of the composition, or that improve a functional property of the composition. The individual composition ingredients are described in more detail below.
The coating composition of the present invention comprises an acrylate copolymer having pendant hydroxy groups in an amount of about 45% to about 90%, and preferably about 50 to about 80%, by weight of nonvolatile material. To achieve the full advantage of the present invention, the coating composition comprises about 55% to about 70% of the acrylate copolymer, by weight of nonvolatile material.
An acrylate copolymer having pendant hydroxy groups that is useful in the present invention contains about 2 to about 50 weight %, and preferably about 3 to about 40 weight %, of a monomer containing a hydroxy group, for example, hydroxyethyl methacrylate. To achieve the full advantage of the present invention, the acrylate copolymer contains about 4 to about 20 weight % of a monomer containing a hydroxy group. Similarly, the alkyl (meth)acrylate is present in the copolymer in an amount of about 50 to about 98 weight %, preferably about 60 to about 97 weight %, and preferably about 80 to about 96 weight %. The copolymer also can contain 0 to 10 weight %, and preferably 0 to 5 weight %, of an optional monounsaturated monomer.
The monomer containing a hydroxy group can be any monomer having a carbon-carbon double bond and a hydroxy group. Typically, the monomer is a hydroxyalkyl ester of an xcex1,xcex2-unsaturated acid, or anhydride thereof. The xcex1,xcex2-unsaturated acid can be a monocarboxylic acid or a dicarboxylic acid. Examples of such carboxylic acids include, but are not limited to, acrylic acid, methacrylic acid, ethacrylic acid, xcex1-chloroacrylic acid, xcex1-cyanoacrylic acid, xcex2-methylacrylic acid (crotonic acid), xcex1-phenylacrylic acid, xcex2-acryloxypropionic acid, sorbic acid, xcex1-chlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinnamic acid, xcex2-stearylacrylic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, tricarboxyethylene, maleic anhydride, and mixtures thereof. As used throughout this specification, the term xe2x80x9c(meth)acrylatexe2x80x9d is an abbreviation for acrylate and/or methacrylate.
Specific examples of monomers containing a hydroxy group are the hydroxy (C1-C6)alkyl (meth)acrylates, e.g., 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, and 3-hydroxypropyl methacrylate.
The acrylate copolymer also initially can be a copolymer of an xcex1,xcex2-unsaturated acid and an alkyl (meth)acrylate, which then is reacted with a glycol or polyol, e.g., ethylene glycol or propylene glycol, to position pendant hydroxy groups on the acrylate copolymer. The xcex1,xcex2-unsaturated carboxylic acid can be an acid listed above, for example.
In an alternative embodiment, an acrylate copolymer having pendant glycidyl groups first is formed. The copolymer then is reacted with a reagent to open the glycidyl epoxy ring and position pendant hydroxy groups on the acrylate polymer. The acrylate copolymer having pendant glycidyl groups can be prepared by incorporating a monomer like glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, or vinyl glycidyl ether into the acrylate copolymer.
A preferred monomer containing a hydroxy group is a hydroxyalkyl (meth)acrylate having the following structure: 
wherein R1 is hydrogen or methyl, and R2 is a C1 to C6 alkylene group or an arylene group. For example, R2 can be, but is not limited to (xe2x80x94CH2xe2x80x94)n, wherein n is 1 to 6, 
any other structural isomer of an alkylene group containing three to six carbon atoms, or can be a cyclic C3-C6 alkylene group. R2 also can be an arylene group, like phenylene (i.e., C6H4) or naphthylene (i.e., C10H6). R2 optionally can be substituted with relatively nonreactive substituents, like C1-C6 alkyl, halo, (i.e., Cl, Bxe2x80x94, F, and I), phenyl, alkoxy, and aryloxy (i.e., an OR2 substituent).
The monomer containing a hydroxyl group, or the monomer that contains a group (like carboxyl or glycidyl) that can be converted to a hydroxyl group, is copolymerized with an alkyl (meth)acrylate having the structure: 
wherein R1 is hydrogen or methyl, and R3 is an alkyl group containing one to sixteen carbon atoms.
The R3 group can be substituted with one or more, and typically one to three, moieties such as halo, amino, phenyl, and alkoxy, for example. The alkyl (meth)acrylates used in the copolymer therefore encompass aminoalkyl (meth)acrylates. The alkyl (meth)acrylate typically is an ester of acrylic or methacrylic acid. Preferably, R1 is methyl and R2 is an alkyl group having two to eight carbon atoms. Most preferably, R1 is methyl and R2 is an alkyl group having two to four carbon atoms. Examples of the alkyl (meth)acrylate include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isoamyl, hexyl, 2-aminoethyl, 2-ethylhexyl, cyclohexyl, decyl, isodecyl, benzyl, lauryl, isobornyl, octyl, and nonyl (meth)acrylates.
Optional monounsaturated monomers suitable for copolymerizing with the monomer containing a hydroxy group (or monomer having a group that can be converted to a hydroxy group) and alkyl (meth)acrylate include, but are not limited to vinyl monomers, like styrene, a halostyrene, isoprene, diallylphthalate, divinylbenzene, conjugated butadiene, xcex1-methylstyrene, vinyl toluene, vinyl naphthalene, and mixtures thereof. Other suitable polymerizable vinyl monomers include acrylonitrile, acrylamide, methacrylamide, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, isobutoxymethyl acrylamide, and the like.
The hydroxy-containing monomer (or precursor thereof), alkyl (meth)acrylate, and optional monounsaturated monomers are polymerized by standard free radical polymerization techniques, e.g., using initiators such as peroxides or peroxy esters, to provide a copolymer having a weight average molecular weight (Mw) of about 4,000 to about 50,000, and preferably about 6,500 to about 40,000. To achieve the full advantage of the present invention, the copolymer has an Mw of about 7,000 to about 25,000. In the preparation of the copolymer, a chain transfer agent, such as isopropyl alcohol or n-dodecyl mercaptan, can be used to control the Mw of the polymer.